CN1158336A - Gas phase polymerization employing unsupported catalysts - Google Patents

Gas phase polymerization employing unsupported catalysts Download PDF

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Publication number
CN1158336A
CN1158336A CN96112025A CN96112025A CN1158336A CN 1158336 A CN1158336 A CN 1158336A CN 96112025 A CN96112025 A CN 96112025A CN 96112025 A CN96112025 A CN 96112025A CN 1158336 A CN1158336 A CN 1158336A
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polymerization process
solvent
gas
catalyst system
reactor
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Inventor
G·E·凯勒
K·E·卡米凯尔
J·B·克普利
E·R·拉森
A·V·拉马穆菲
M·W·施美尔
T·T·温策
C·C·威廉斯
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the gas-phase polymerization of polymers which allows for the introduction of an unsupported polymerization catalyst system into the gas-phase reactor, wherein the unsupported polymerization catalyst system comprises (i) a non-volatile materials fraction containing a polymerization catalyst; (ii) a solvent fraction which is at least partially miscible with the non-volatile materials fraction and which is sufficiently volatile to allow for the formation of polymerization catalyst particles when the mixture of the solvent fraction and the non-volatile materials fraction is sprayed into the reactor; (iii) a compressed fluid; and (iv) optionally a slowly vaporizing solvent.

Description

Use the vapour phase polymerization of unsupported catalysts
The present invention relates to use the vapour phase polymerization of unsupported catalysts, especially the present invention relates to use overcritical or the high compression fluid as the means of unsupported catalysts being sought into gas phase.
It is not only complicated but also important course in whole process that catalyzer imports gas-phase polymerization reactor.This course must be considered not only the chemical reaction that begins when catalyzer and monomer meet, but also will consider the engineering aspect that this conveying course how to occur.In the polyolefm chemistry field, produced new discovery for the design of various carrier catalysis agent methods and delivery nozzles.The principle major part that is later than these discoveries is based on a kind of like this supposition, and promptly carrier revolves and supplies the growth of polymer particle to cause required product form, and plays and reduce to greatest extent and the relevant operational issue of the non-solid catalyst particle of importing.
Catalyzer has been immersed on carrier such as the silicon-dioxide and has imported in the reactor, carries out gas-solid polyreaction in this reactor.Support of the catalyst in batching and other solid mortise of possibility are in resin, and proof is harmful to some resin properties.For example, film clarity may be subjected to having excessive solid in the resin and reduce.In addition, the use of support of the catalyst causes having the catalyst position of different chemical character, therefore causes the polymkeric substance more different than formation with the polymer phase that forms on other catalyst position.As a result, the resin of generation is the different mixture of polymers that form on different positions.The use of unsupported catalysts is eliminated by caused problem of existing of support of the catalyst, and represents catalyzer to import the new technology of polymerization reactor.
Recently, in the polymeric chemical field, found to have the very catalyzer of high reactivity (if after all being transformed into productivity).It has the trend that strengthens polymerization process.As what advised in these reference, the catalyzer that is formed by transistion metal compound and aikyiaiurnirsoxan beta has much higher activity than the previous polymerisation catalyst system that is formed by transistion metal compound and organo-aluminium compound that uses.These catalyst systems of great majority are to dissolve in the reaction system and be used for solution polymerization system.As a result, it is very high that the viscosity of polymers soln becomes, and the polymkeric substance that is obtained by the solution aftertreatment has low bulk density, and this method is difficult to obtain having the polymkeric substance of good characteristic.
On the other hand, comprise above-mentioned transistion metal compound, or aikyiaiurnirsoxan beta or both for example are loaded in the porous inorganic oxide carrier: silicon-dioxide, the catalyzer on silica-alumina or the aluminum oxide by use.In suspension polymerization system or gas phase polymerization system, carry out olefin polymerization and carried out various trials, see for example US4897455,4937301,5147949 and 5373072.
Also reported the trial of eliminating as generating the inorganic carrier that impurity prepares in the polymkeric substance, this polymkeric substance is obtained by the general catalyzer that is loaded on the inorganic carrier.See US4923833, wherein use the agent of solid fine grain muonic catalysis not have carrier.
Recently, some that have been found that these catalyzer keep its high reactivity (seeing US5317036) when in the reactor of packing into as solution.In addition, new discovery has recently shown in vapour phase polymerization, is not only and might operates (seeing US4543399 and 4588790) in condensing mode.And advantageously use in some cases and add liquid monomer (US5453471).These factors have caused making in vapour phase polymerization uses liquid catalyst than more important before thenceforth.Therefore, need overcome the intrinsic problem relevant with vapour phase polymerization that unsupported catalysts is packed into.
Use compressed fluid that scientific research is become main field in the new application, mainly in field of solvents in order to carry out various separation, the batching and the technology (seeing US4916108,5326835 and 5391654) of carrying coating to use.
Use is that catalyzer imports the good means of reactor as the supercutical fluid or the compressed fluid of a catalyst formulation part, and unexpected discovery solves and the relevant many problems of interpolation unsupported catalysts in gas phase polymerization.
The invention provides a kind of method of polymkeric substance vapour phase polymerization, this method comprises that a kind of monomer or multiple monomer and non-carrier polymerisation catalyst system import in the Gas-phase reactor, and wherein non-carrier polymerisation catalyst system comprises the non-volatile substance part that contains polymerizing catalyst; Solvent is (described solvent partly mixes and the formation polymerizing catalyst particle that is enough to volatilize when spraying to small part is solvable with the non-volatile substance part) partly.The high compression fluid; With arbitrarily slow evaporating solvent; And recovery polymer product.Might work as and use promotor for example during aikyiaiurnirsoxan beta, for example add in the reactor with monomer feed with non-high compression fluid.The catalyst particle that forms can exist or exist with the drop form by solids, wherein solids by wet with solvent or even herein catalyzer still in solution.
Provide as the use of the supercutical fluid of a catalyst formulation part or compressed fluid polymerization is imported Gas-phase reactor with unsupported catalysts, for example UNIPOL Strong means in the polyolefin reactor.Have found that and use compression or supercutical fluid to produce the spray pattern that remarkable superior drop is gone into Gas-phase reactor, wherein form the additional thus growth of particle that new polymer beads and prevention are increasing.Especially compressed fluid spraying has much narrow droplets size distribution.The major portion of drop is undersized.Surprising is that these small dropletss do not generate soot particle, and produces the narrow distribution of polymer particle size.
According to the present invention, provide the method in a kind of strong unsupported catalysts importing Gas-phase reactor newly.
When the temperature of neat liquid raise, this liquid became steam.Therefore, when a normal atmosphere heated, water just became steam at 100 ℃.If pressure raises, water does not become steam until water reaches higher temperature and just becomes steam so.Along with the further increase of pressure will produce more and more high-temperature, liquid water just becomes steam.Yet this situation has a restriction.Under 3208.2psia and 374.15 ℃, water reaches so-called its stagnation point, and at this point, steam and fluid density equate.In addition, surpass 374.14 ℃, can not produce liquid phase if temperature is raised to.No matter how high institute's applying pressure is.374.14 ℃ temperature claim the critical temperature of water, 3208.2psia claims the emergent pressure of water.
As used herein, it will be appreciated that " compressed fluid " can be gaseous phase, liquid state or fluid that both combine, or supercutical fluid.Depend on the specific temperature and pressure that (i) applies, (ii) fluidic vapour pressure and (iii) fluidic critical temperature and emergent pressure under this specified temp.But under standard conditions, i.e. 0 a ℃ of temperature and a BAP Barometric Absolute Pressure (STP), fluid is to be gas.Just as used herein, " supercutical fluid " is to be fluid under stagnation point or the above temperature and pressure of its stagnation point.
Can comprise (but being not limited to) carbonic acid gas, nitrogen protoxide, ammonia, xenon, ethane, ethene, propane, propylene, butane, Trimethylmethane, chloro-trifluoro-ethane, a fluoromethane and composition thereof as the compound of compressed fluid of the present invention.In table 1, list some gaseous matters commonly used with and critical temperature and pressure.Should notice that the conventional boiling point of material is low more in general, its critical temperature is low more.Preferably the critical temperature of compressed fluid is greater than 273K and less than 505K.
Table 1
The example of supercutical fluid
Compound boiling point critical temperature emergent pressure critical density
℃ ℃ normal atmosphere g/ml
Ethene-103.7 9.2 49.7 0.22
Xenon-108.2 16.6 57.6 0.12
Chloro-trifluoro-ethane-31.2 28.0 38.7 0.58
Carbonic acid gas-78.5 31.3 72.9 0.45
Ethane-88.6 32.3 48.1 0.20
Nitrogen protoxide-88.6 36.5 71.7 0.45
One fluoromethane-78.4 44.6 58.0 0.3
Propane-42.1 96.7 41.9 0.22
Ammonia-33.4 132.4 112.5 0.24
At table among the l in the listed compound, carbonic acid gas is the most normal illustration that uses as compressed fluid that is mentioned in various separation and other process.For example, UNICARB TMThe general carbonic acid gas that uses in the overcritical spraying method.But for many catalyzer, carbonic acid gas can partly or entirely make poisoning of catalyst.Therefore, when carrying described catalyzer, may be to use other fluid situations.Fluid both may be inert or reactive monomer or other intermediate.
The example of inert fluid is ethane and propane.The example of active fluid is ethene and propylene.It should be noted that catalyzer and promotor, for example metallocenes and aikyiaiurnirsoxan beta can have under the initiated polymerization simultaneously in active fluid.The compressed fluid of selecting is steam under the pressure and temperature of reactor.In enforcement of the present invention, the catalyzer of conveying is depended in the use of any above-mentioned compressed fluid, the temperature and pressure of reactor, compressed fluid inertia and stability.
The catalyzer batching is to contain solvent composition basically.Contain solvent catalyst and generally comprise (1) and contain, can generate the non-volatile substance part of the polymerisation catalyst system of particle when when spraying; (2) solvent part, it can mix mixed to small part and non-volatile substance, and is enough to volatilization when spraying, makes the described solvent catalyst that contains can form particle.But whole solvent evaporations just take place in this in general, when solvent evaporation less than 100% the time during, promptly polymerizing catalyst keeps as fine drop.Described spraying is to take off compression spraying.Although for obtaining advantage of the present invention is not absolute crucial.
In general, non-waving property material part be solvent evaporate partly that the back keeps contain the solvent catalyst part, so it is the part that forms particle.Be fit to the non-volatile substance part, comprise (but need not be limited to following) metalloscene catalyst, catalyzer is put by other unit.Ziegler-Natta catalyst, aikyiaiurnirsoxan beta, borate.Organoaluminum promotor and be present in other component in the catalyst system usually.
The example of enumerating of described suitable catalyst comprises two (cyclopentadienyl) zirconium dichloride/methylaluminoxane; Two (indenyl) zirconium dichloride/methylaluminoxane; Two (butyl cyclopentadienyl) zirconium dichloride/methylaluminoxane, titanium tetrachloride/triethyl aluminum.The non-volatile substance part can be carried as solution, emulsion, dispersion liquid or suspension in the solvent part.Preferably be that non-waving property material part is carried as solution.In general, the size of particles that has of dispersive separate solid is enough little of to keep dispersion state and to be easy to by the delivery nozzles hole.If stir and to form and to keep dispersion or suspension, can use to have the too big separate solid that consequently can not keep stabilising dispersions of size of particles.
Non-volatile thing is generally partly that to contain solvent catalyst weight about more than 0.01%, be preferably greater than about 0.05%, more preferably greater than about 0.1%, most preferably greater than about 1%.Non-volatile substance part can not so undue high part contains solvent catalyst and can not form and take off compression spraying or formation suitable particles size basically to cause.The suitable upper limit depends on the physics-chem characteristic of selected specific non-volatile substance part, for example in molecular weight and solubleness.It is about 70% that non-volatile substance partly is generally less than, be more preferably less than about 50%, most preferably less than about 40%.
In general, solvent part preferably less than containing the about 99% of solvent catalyst weight, is more preferably less than 60%, and most preferably less than 50%, solvent should be a rapid evaporation.The boiling point that the solvent of rapid evaporation generally has is between 225K and 400K.The solvent of selecting is that part is miscible and have enough volatility with non-waving property material at least.Higher solubleness is preferred.Solvent preferably is complementary with the catalyst activity of preserving and the solubleness of catalyst substance.Suitable solvent comprises (but being not limited to) iso-pentane, high boiling point monomers for example hexane and octane, and the carbon atom number is up to 8 solvent (not being oxygen containing solvent).In some cases, catalyzer exists with the high reactivity state in its first second of life-span or several minutes.In general, before this high reactivity initial stage finished, compressed fluid evaporated fully from drop, can cause catalyst particle to be vulnerable to overheated and took off work.This problem can overcome by add slow relatively evaporating solvent in batching.Generally more than 400K, the typical case is slow, and evaporating solvent comprises that (but being not limited to) carbon number is at the solvent more than 8, C to the boiling point of slow evaporating solvent 2Or bigger oxo alkane, high boiling point monomers and mineral oil.This solvent forms diffusion barrier when monomer arrives catalyzer, and has also increased the drop external area.These factors slowly reduce reaction, the heat transfer rate that increases drop alleviates the high reactivity problem thus, the amount of slow solvent (if having) is that benchmark can be up to about 70% (weight), preferably about 0-60%, most preferably from about 0-50% with compressed fluid, the gross weight that contains solvent catalyst and slow solvent.
For spraying, in closed system, contain solvent catalyst and at first mix forming liquid mixture with at least a compressed fluid, the amount of compressed fluid should make liquid mixture form to take off compression spraying basically.In general, to contain solvent catalyst be at compressed fluid and contain between 0.01 to 99.99% (weight) of solvent catalyst gross weight, is preferably 0.05 to 75% (weight), most preferably is between 0.1 to 40% (weight).Then liquid mixture is taken off under the temperature and pressure of compression spraying basically in generation, mixture is sprayed into reactor by orifice, in reactor, form particle.Some liquid solvents can moistening solid particle surfaces or even are replaced the catalyzer in the solution and keep with the particulate drop as mentioned above.Basically take off compression spraying and generally in the scope that is rather narrow that compressed fluid concentration and vapo(u)rizing temperature and pressure combine, form, and change with the specific characteristic variations that contains solvent catalyst.Key character is the composition and the amount of non-volatile part, the composition of solvent and the composition of used compressed fluid.Therefore, for any given spray mixing thing and orifice, the condition that compression spraying is taken off in suitable formation basically generally must be determined by experiment.Yet, take off the compression spraying district and generally should be lower than the solubility limit of compressed fluid in containing solvent catalyst, and change with the variation of pressure and temperature.As disclosed in the US number of patent application 129256 that subjects to approval of application in 1993 9.29.Under constant voltage, solubleness reduces when high temperature.Solubleness increases with high pressure.Take off the compression spraying district and generally appear at compressed fluid concentration a shade below the solubility limit place, this limit is usually in about 5% (weight) or more among a small circle.Spraying is usually just in time carried out being lower than under the solubility limit.Use sufficiently high spray pressure to obtain enough high-dissolvabilities.Regulate vapo(u)rizing temperature and compressed fluid concentration then to provide the compression spraying that takes off with required drop size.Solubleness also changes and changes along with used compressed fluid.Solubleness also changes and changes along with the level of non-volatile substance part, and is lower for high-content solubleness.When the above compressed fluid concentration of solubility limit, when high pressure, liquid mixture generally comprise the liquid non-volatile substance mutually and the liquid compressed fluid of the solvent that contains extraction mutually, and when low pressure, excessive compressed liquid formation gas phase.
In general, the amount of used compressed fluid is with compressed fluid and contain the solvent catalyst gross weight and count about 1 to 99.99% (weight), preferred about 3 to 99.95% (weight), most preferably from about 5 to 99.9% (weight).The amount of compressed fluid can surpass solubility limit (as needs), but should be too not high so that excessive compressed fluid too disturb spraying to form mutually for example in the solution mixture, can not to keep good distribution or give the nebulization of going on business.If desired, can use excessive compressed fluid before spraying, to separate the solvent part (using the US5290604 disclosed method) of spray mixing thing.Liquid mixture generally contains less than about 60% (weight) compressed fluid.
Although can use spray pressure to reach more high pressure up to 10000psig, the spray pressure of preferred liquid mixture is lower than about 5000psig, more preferably less than about 3000psig.Very the general and solubleness of high compression fluid in containing solvent catalyst of low pressure does not match.And with vapour phase polymerization in the super-atmospheric pressure that run into do not match.
Supercutical fluid preferably under the pressure and temperature of compressed fluid when the spraying liquid mixture.Although to the solvent of the evaporation of fast spraying more, higher vapo(u)rizing temperature is favourable, temperature must be complementary with keeping catalyst activity, because some catalyst substances are to warm, and thermo-responsive in the special solvent.Therefore, it generally is preferred awarding required minimum spray temperature of taking off compression spraying and suitable solvent evaporation.Operable temperature levels generally depends on the characteristic that contains solvent catalyst.For example stability and heat sensitivity.Reactive systems generally must spraying when hanging down than the temperature of nonactive system.Preferably the vapo(u)rizing temperature of liquid mixture is between about 0 to 130 ℃, more preferably from about between 20-100 ℃, most preferably from about between 30-85 ℃.In order to improve the vaporator rate of spraying solvent, liquid mixture preferably is heated to compensation basically and the temperature that vapo(u)rizing temperature descends occurs owing to take off the diffusion cooling of the compression system body of compression.Basically take off compression spraying generally by the compressed fluid quantitative changeization produces in the temperature range and forms with changes in solubility.Rapider in order to make to form particle from the solvent vaporization of spraying, need to use higher vapo(u)rizing temperature.For the average vaporator rate relatively of solvent for use part and the quantity of solvent that must evaporate, vapo(u)rizing temperature should be enough high to improve enough fast solvent and compressed fluid evaporation.For than the relative vaporator rate of harmonic(-)mean, general higher vapo(u)rizing temperature is preferred.
The catalyst particle that is formed by the inventive method need have the about 0.1-20 micron of average particulate size scope, is preferably about 5-15 micron.The most favourable size of particles depends on specific polyreaction of carrying out and selected catalyst system.In general, narrow particle size distribution is preferred.
Typical catalyst contains at least a transistion metal compound.Be sure of that the present invention finds to be called the unusual practicality of the catalyst type of metallocenes.That some preferred catalyst systems comprise is two-just-the butyl cyclopentadienyl zirconium dichloride, indenyl carboxylamine diethyl ester zirconium, or indenyl PIVALIC ACID CRUDE (25) zirconium.Preferred promotor comprises MAO (methylaluminoxane) or modification MA0, and it is made up of the methylaluminoxane of the methyl alkyl part that contains useful isobutyl-replacement.The solvent of preferred L AO is a toluene, is iso-pentane for the solvent of MMA0.Preferred slow solvent is propylene or mineral oil.Compressed fluid is ethane or propane preferably.
Preferred catalyst body ties up under the pressure and temperature of delivery nozzles ingress only by a phase composite.But when by delivery nozzles, might form two-phase and required gas phase.
Orifice is that a hole or opening are in wall or in the chamber, for example in delivery nozzles.Spray holes, spraying tip, fog nozzle, atomizer and kapillary generally are fit to spraying liquid mixture of the present invention.Delivery nozzles does not have excessive flow volume between orifice and spray switch valve, it is preferred also not hindering wide-angle (generally there is spray holes in spraying herein).About 0.001 inch to the 0.0625 inch specific diameter of orifice size is preferred, although can use less and big orifice size.Recently, commerical prod only is low to moderate 0.003 diameter, but believes that low diameter also is useful.Also can use before mixture passes through orifice, promote the turbulent flow in the liquid mixture or stir stream device and flow design, for example orifice or turbulent flow are promoted device in advance.Pre-orifice can not produce preferably that excessive pressure falls in the liquid mixing logistics.Spray pattern can be that circular spraying for example produces or oval or flat spraying with circular hole, as producing (as above-mentioned) by groove by orifice.Contain solvent composition or high vaporator rate relatively for special thickness, more oval or circular spraying can wish to obtain at spraying point place least polymkeric substance result.Other design has two mutual rectangular grooves.Export by orifice.Producing more, the two cross spray fan of rotational symmetry spray pattern obtains being mixed into spraying inside than the better environmental gas of circular orifice.Pressure in Gas-phase reactor must be lower than spray pressure basically, so that obtain the compression of taking off of enough compressed fluids, take off compression spraying with formation, reactor should contain the enough low high compression fluidic dividing potential drop that is contained in the solvent composition, to promote from the evaporation of spraying solvent rapid enough.Very low dividing potential drop is preferred.However, the present invention can operate in shortening pattern and super shortening pattern.
Take off compression spraying and produce the even spraying pattern, have narrow particle size distribution.Not only particle size distribution is narrow in spraying place, and average particulate size is very even at horizontal spray pattern, and this just obtains the narrow all particles distribution of sizes of whole spraying, is exactly time to atomize because some zones were not atomizings.Inhomogeneous atomizing usually brings some problems of general spray method.
Gas phase polymerization is in gas phase process, and for example in following bed process, essentially no catalyzer poison is being enough under the initiated polymerization temperature and pressure, makes monomer air-flow contact and carries out.Be fit to whole vapour phase polymerizations although believe the present invention, consider that working as monomer (or multiple monomer) is C 2To C 10When straight or branched alkene, diolefine or alkatrienes is particularly useful.Most preferred monomer is selected from ethene, propylene, butylene, amylene, alkene, octene and 1,3-butadiene.
The fluidized bed reaction system that can be used for the inventive method enforcement has the reactor of being made up of reaction zone and speed attenuating district.
Reaction zone comprises the polymer particle that is increasing, the bed of polymer particle that has generated and little amount of catalyst particle, and this is by passing through the polymerizable of reaction zone and the Continuous Flow fluidisation of modified gas component with additional material and recycle gas form.For keeping to keep fluidized-bed, material gas flow rate by bed must be more than the required minimum flow rate of fluidisation, preferred 1.5 times to about 10 times of Gmf, more preferably about 3 to about 6 times of Gmf, the Gmf that uses reaches the acceptable abbreviated form of the required minimum material gas stream of fluidisation (C.Y.Wen. and Y.H.Yu, " Mechanics of Fluidization, ChemicalEngineering Progress Symposium Series; Vo1.62, p.100-111 (1966).
Must bed always contain particle with prevent to form local " focus " and interception catalyzer and with catalyst distribution in the entire reaction district.When driving, reactor was equipped with a bottom particulate polymers particle usually before gas stream is introduced.Described particle in itself can be identical or different with the polymkeric substance that will form.When not simultaneously, reactor discharges required formation polymer particle as first product.At last, the fluidized-bed of required polymer particle replaces the beginning bed.
Be circulated in bed and reach fluidisation by high-speed gas by bed, this speed general about 50 times to compensation gas feeding rate.Fluidized-bed has total outward appearance of keeping fluidized bed close material may not having in the eddy current.This is to be produced by the infiltration of gas by bed.Pressure by bed fall be equal to or slightly greater than bed quality divided by cross section.Therefore this just depends on the geometrical shape of reactor.
The speed that supply gas is sent in the bed equals particulate polymers product drainage rate.The composition of supply gas is determined by the gas-analysis apparatus that is positioned at a top.Gas-analysis apparatus is determined that recycle gas is formed and is regulated the composition of supply gas according to keeping in the reactor steady state gas composition basically.
In order to guarantee complete fluidisation, recycle gas and (as needs) part supply gas through the gas circulation pipeline at the bottom of bed Returning reactor.But the using gas distribution plate helps this bed of fluidisation on the place of returning.
Responseless portion gas stream constitutes recycle gas (it is removed by polymerization zone) in the bed, preferably its speed by bed top is lowered the district, in this district entrained particles is obtained a chance and falls into bed.
Recycle gas compresses in compressor and passes through heat exchanger more then, and hereinto, recycle gas removed its reaction heat before returning bed.Note condensation mode (enumerating).Under steady-state condition, be in the substantially constant temperature by removing reaction heat control bed tempertaure with keeping.The remarkable thermograde that in the top of bed, does not have appearance.Thermograde exists in the bottom of bed, in the temperature of inlet gas and the lathe between the retention temperature.Recycle gas is gone into reactor and is gone into fluidized-bed by distribution plate at reactor bottom then.Compressor also can be provided with downstream heat exchanger.
Distribution plate plays an important role in the operant response device.Fluidized-bed contain increasing with established particulate polymers particle and catalyzer.When polymer particle be heat and when having activity, must prevent the polymkeric substance sedimentation, if static material allows to exist, any active catalyst that then is included in wherein may continue reaction and cause fusing.Again this, the speed of the diffusion recycle gas by bed is enough to keep the whole bed fluidisation, this point is important.Distribution plate is served this purpose, and it can be a sieve plate, slotted plate, orifice plate, bubble-cap template or the like.The element of plate can all be a fixed, or plate can be active (as disclosed among the US3298792).No matter how it designs, and necessary diffusion recycle gas particle bottom bed is in fluidized state with the maintenance bed.It also play when reactor not at the resin particle bed of when operation supported in rest.The moving element of plate can be used to move any cross section and stays in the plate or the polymer particle on the plate.
Operating fluidized bed reaction is carried out under the sintering temperature of polymer particle to guarantee sintering not occur being lower than basically.For producing Alathon and multipolymer, about 0 ℃ to 150 ℃ of general application operating temperature, preferred about 10 ℃ to 140 ℃, most preferably from about 30 ℃ to 115 ℃.
The fluidized-bed reactor working pressure is up to arriving 1000psi, preferably operate under the about 50-700psi of pressure, more preferably from about 100 to 600psi, most preferably is about 150 to 350psi, carry out under the elevated pressures and will help heat exchange when operating in, increase because pressure increases the heat capacity per unit volume of gas.
The catalyzer speed of injecting reactor equals its wear rate.Catalyzer can inject the top or the bottom of fluidized-bed or bed, and this will depend on the character of the catalyst system of spraying, and flow rate mode in the bed should not be disturbed at the position of injection.Preferably the position is on the top of distribution plate, and about 1/4 to 1/2 catalyst particle forms main or new resin particle, to keep required resin particle distribution of sizes.Portion's charging catalyzer provided long-time catalyst particle drying before covering the resin particle that has existed in bed.In addition, also catalyzer can be sent in the bed, but at first by importing the pipeline of reactor, this just becomes essentially no solvent to particle and uses the time.
The productivity of bed is by the control of catalyzer rate of injection, and productivity can improve by simple increase catalyzer rate of injection, and can reduce by lowering the catalyzer rate of injection.
Because any variation of catalyzer rate of injection will change the generating rate of reaction heat, the recycle gas temperature that therefore will enter reactor generates or hot rate variations to raising or reduce adapting to.This just guarantees to keep the substantially constant temperature in the bed.Certainly any temperature variation makes the operator suitably regulate the temperature of recycle gas with activation in the bed to detect to need fluidized-bed and the complete instrument of recycle gas cooling system.
Under the operational condition of determining, the generating rate that equals particulate polymer product by the speed as product discharge unit bed keeps fluidized-bed substantially constant height, it is directly relevant with the product generation to be used for hot generating rate, passes the measurement of gas reactor temperature rising (poor between inlet gas temperature and the Outlet Gas Temperature) and determines particulate polymers generating rate under constant gas speed.
Particulate polymer product is preferably in distribution plate or discharges continuously near the distribution plate place, the further polymerization that produces minimum degree when being the particle precipitation of suspensoid with the portion gas stream of discharging, and when particle arrives its last collecting region the ability sintering.The gas that suspends also can be used to drive the product of a reactor in another reactor.
Embodiment
Exact range of the present invention is listed in the appended claims, and method of the present invention is especially pointed out to estimate in following specific embodiment explanation some aspect of the present invention.But embodiment only is explanation, does not think restriction the present invention (except that as listed in the appended claims).All umbers and percentage ratio are except as otherwise noted all by weight.Embodiment 1: examine compressed fluid embodiment as the spray that the spraying delivery nozzles uses
Have 0.007 " and the atomizer of inch orifice (Model TP 400008 TC) (ModelAA24AUA-8930-36; by providing; be fit into 14 in the Spraying of Wheaton IL Systems company " side of diameter Gas-phase reactor, approximately about 4 inches apart from dispenser panel, stretch into reactor 1-3 inch, reactor has fan-spray perpendicular to the monomer flow direction, and promptly fan-spray is a level by bed vertically for monomer flow.Reactor begins packed bed with polyvinyl resin, monomer dividing potential drop 220psi, the dividing potential drop 4psi of hexene.
The spraying e Foerderanlage begins with 0.004wt% indenyl tertiary butyl carboxylicesters (corboxylate) zirconium and 0.21wt% modified methylaluminoxane catalyzer, 0.1wt% hexane, 2.6wt% ethane and the filling of body iso-pentane.When operation was carried out, the beginning catalyzer was selected materials and is introduced in the reactor, sends into the spraying e Foerderanlage subsequently, near adding the beginning charging.
The pressure of spraying e Foerderanlage determines that at 1000psig, temperature is uncontrolled in room temperature; At run duration, temperature is between 298K and 308K.The melt index of the resin of producing be 0.481 degree/minute, tap density is 18.5 pounds/foot 3, resin density 0.917g/cc, 0.018 inch of average particulate size.When running abort, operation shows the fine powder content of surprising reduction 2.1wt%.Embodiment 2: the use supercutical fluid embodiment that is used as the spray capillary of nozzle
20cm is long, 1/16 " OD, 0.005 " the stainless steel tube silver soldering of ID be connected on outer support 1/8 " in the stainless steel tube of OD.This is 1/8 years old " * 0.005 " guard system is placed on about 10.5 " about 3-5 on the distribution plate in the Gas-phase reactor " locate.Flow through kapillary and 3/4 with 2 to 5 Pounds Per Hours of nitrogen around this tip " surrounding space between stainless steel tube.3/4 " pipe extension 2-3/4 inch is gone into reactor.3/4 " pipe around 3/4 " inch pipe and 1 " flow through 1800 Pounds Per Hours of recycle gas in the circuferential spacing between the ID stainless steel tube.1 " pipe extends into reactor 2 ".
The spraying e Foerderanlage is used 0.063wt% indenyl tertiary butyl carboxylicesters (corboxylate) zirconium and 5.5wt% modified methylaluminoxane catalyzer, 7.6wt% ethane and the feeding of body iso-pentane at first.The fluidic temperature is fixed on 46 ℃ in the spraying delivery system, and pressure fixing is at 1000psig.As same procedure as described in the embodiment 1, initial start reactor.
The resin of producing have melt index 0.404 degree/minute, tap density is 12.3 pounds/foot 3, resin density is 0.930g/cc, average particulate size is 0.0248 inch.This running shows the content that exceeds unexpected reduction fine powder 0.2wt% again.Embodiment 3: the use supercutical fluid embodiment that is used as the spray capillary of nozzle
20cm is long, 1/16 " OD, 0.007 " the stainless steel tube silver soldering of ID be connected on outer support 1/8 " in the stainless steel tube of OD, this is 1/8 years old " * 0.007 " guard system is placed on about 10.5 " Gas-phase reactor in about 2-3/4 on the distribution plate " locate.Cross kapillary and 3/4 with 2 to 5 Pounds Per Hours of nitrogen gas stream around this tip " surrounding space between stainless steel tube.3/4 " the inch pipe extends into 2 inches of reactors.3/4 " around the pipe, at 3/4 inch pipe and 1 " flow through 1800 Pounds Per Hours of recycle gas in the surrounding space between the ID stainless steel tube.1 " pipe extends into reactor 2 ".
The spraying e Foerderanlage is used 0.16wt% indenyl tertiary butyl corboxylate zirconium and 8.9wt% modified methylaluminoxane catalyzer at first, 31wt% ethane and the feeding of body iso-pentane, the fluidic temperature is fixed on uncontrolled room temperature in the spraying delivery system, promptly between 298K and 308K, pressure fixing is at 1000psig.Press embodiment 1 described same procedure entry into service reactor.
The resin melt index of producing be 0.833 degree/minute, tap density is 14.8 pounds/foot 3, resin density is 0.926g/cc, and average particle diameter is 0.0337 inch, and this operation exceeds accident and shows the content that reduces fine powder 0.7tw%.

Claims (16)

1. the gas phase polymerization process of a polymkeric substance, this polymerization process comprises:
A) one or more monomers are imported in the Gas-phase reactor,
B) non-carrier polymerisation catalyst system is imported in the Gas-phase reactor, wherein non-carrier polymerisation catalyst system contains:
(i) contain the non-volatile substance part of polymerizing catalyst;
(ii) solvent part, this solvent are to small part and non-waving property material is miscible and have enough volatilizations when solvent part and non-volatile substance mixture partly are sprayed into reactor is convenient to form the polymerizing catalyst particle;
(iii) compressed fluid; With
(iv) arbitrarily slow evaporating solvent;
C) reclaim polymeric articles.
2. the polymerization process of claim 1, wherein monomer or multiple monomer comprise C 2To C 10Straight or branched alkene and diolefine and alkatrienes.
3. the polymerization process of claim 2, wherein monomer is ethene, propylene, butylene, amylene, alkene, octene and 1,3 divinyl.
4. the polymerization process of claim 1, wherein catalyst system contains at least a transistion metal compound.
5. the polymerization process of claim 4, wherein catalyst system is a metallocenes.
6. the polymerization process of claim 1, wherein solvent is the straight or branched alkane less than C8.
7. the polymerization process of claim 1, wherein evaporation is greater than C slowly 8Straight or branched alkane or greater than C 2The solvent of oxo alkane.
8. the polymerization process of claim 1, the critical temperature of wherein compressed fluid, or fluid mixture is greater than 273K with less than 505K.
9. the polymerization process of claim 1, wherein compressed fluid is selected from carbonic acid gas, nitrogen protoxide, ethane, propane, ethene, oxygen Halothane, single fluoromethane, ammonia and xenon.
10. the polymerization process of claim 1, wherein catalyst system is to import reactor at pressure less than under the 10000psig.
11. the polymerization process of claim 10, wherein pressure is less than 3000psig.
12. the polymerization process of claim 1, wherein non-waving property material part are greater than 0.01% (weight) with less than 70% (weight) polymerisation catalyst system.
13. the polymerization process of claim 12, wherein non-waving property material part is greater than 1.0% with less than 40%.
14. the polymerization process of claim 1, wherein the part of the solvent in the polymerisation catalyst system is less than 95% (weight).
15. the polymerization process of claim 1, wherein in the polymerisation catalyst system amount of compressed fluid between 1% and 99.99% (weight).
16. the polymerization process of claim 15, wherein in the polymerisation catalyst system amount of compressed fluid between 5% and 99.9% (weight).
CN96112025A 1995-09-25 1996-09-24 Gas phase polymerization employing unsupported catalysts Pending CN1158336A (en)

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